CN106669814B - A kind of preparation method of ZSM-48/Y composite molecular screen - Google Patents
A kind of preparation method of ZSM-48/Y composite molecular screen Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of ZSM-48/Y composite molecular screen, including following content: (1) ZSM-48 molecular sieve being carried out high-temperature roasting, then unsaturated olefin is contacted with the ZSM-48 molecular sieve after roasting, roasting carbon deposit reaction is carried out in an inert gas atmosphere, then ZSM-48 molecular sieve surface dealumination treatment is carried out, -48 molecular sieve of modified ZSM-5 is obtained；(2) -48 molecular sieve powder of modified ZSM-5, silicon source, sodium hydroxide and water are uniformly mixing to obtain reaction mixture gel system, are aged in confined conditions, then crystallization, finally cooling, washing, dry and roasting obtain ZSM-48/Y composite molecular screen.The composite zeolite molecular sieve of this method preparation organically combines the isomery performance of ZSM-48 molecular sieve with the cracking performance of Y type molecular sieve, can be applied in hydrocracked petroleum refining process produce High Quality Lube Base Oils.
Description
Technical field
The present invention relates to a kind of composite molecular screen and its synthetic technologys, in particular relate to a kind of compound point of ZSM-48/Y
The preparation method of son sieve.
Background technique
Into after 21 century, the production of API I class base oil and using will greatly reduce, the API II of hydrogenation method production
The situation that supply falls short of demand will be will appear with API Group III base oil, capacity and output is by rapid development.According to estimates 38%
Paraffin base oil will pass through isomerization dewaxing or other catalytic dewaxing technologies production.
Hydrocracking tail oil is the raw material of good lube base oil production, external always to pay attention to utilizing being hydrocracked tail
Oil production lube base oil, can expand the production energy of lube base oil without expansion crude oil vacuum distillation apparatus scale
Power improves fuel type hydrocracking unit operating flexibility, improves the yield and quality of lube base oil.SK company, South Korea
Ulsan, Bombay,India Bharat Petroleum company are referred to using fuel type hydrocracking tail oil production high quality hyperviscosity
Number lube base oil, ExxonMobil Singapore Jurong oil plant are then to produce fuel using lube oil hydrogenation cracking unit
And base oil.The distinctive feature of the technology be hydrocracking tail oil recycle and fuels hydrocracker and lubricating oil processing
The combination of process, products scheme is more flexible, all very economical to the production of fuel and lubricating oil.
Aromatic hydrocarbons more in raw material and cycloalkane can be added using hydrocracking process by hydrogen open loop, generate monocyclic naphthenes and
Alkane.There is low-sulfur, low nitrogen, low arene content, excellent heat peace using the lube base oil of hydrocracking tail oil production
The advantages that qualitative and oxidation stability, lower volatility, excellent viscosity temperature characteristic and good additive response, Ke Yiman
Requirement of the foot modern times top-grade lubricating oil to II/III class base oil of API.And wherein viscosity temperature characteristic is to measure basic oil quality very
Important index, requirement of the more high-grade lube base oil to viscosity temperature characteristic are higher.
The composition and structure of lubricating oil viscosity index and its hydrocarbon-containifirst have close relationship.The viscosity of different hydrocarbons refers to
Number is quite different.Even if being made of identical hydrocarbon system, viscosity index (VI) also has a difference, this difference be by hydro carbons of the same clan in structure
There is caused by difference.It is best with the viscosity temperature characteristic of alkane in hydro carbons contained by lubricating oil, as the viscosity of n-alkane refers to
Number is up to 180 or more.The viscosity index (VI) of isoparaffin is lower than n-alkane, and branch degree more high viscosity refers to lower, band side
The chain index of chain is lower, and the viscosity index (VI) of cycloalkane and aromatic hydrocarbon with side chain is then related with its structural group composition, alkane in molecule
When base portion point is dominant, viscosity temperature characteristic is good, there is higher viscosity index (VI).Monocycle hydro carbons with carbon atom number in molecule increase,
Viscosity index (VI) increases, and bicyclic and polycyclic hydro carbons, viscosity index (VI) also increases with the increase of the number of side chain and length, polycyclic short
The viscosity temperature characteristic of pendant cyclic hydrocarbon is worst.M.ushi. the equal viscosity index (VI) with linear regression analysis processing hydrotreating base oil
And composition data, the viscosity index (VI) of different the hydrocarbon components in lubricating base oil is obtained, the viscosity index (VI) of each component is according to one ring of alkane
The sequence of one aromatic hydrocarbons of alkane reduces.Such as the viscosity index (VI) of the different hydrocarbons of following table.
From the viscosity index (VI) feature of above-mentioned various hydro carbons it follows that isoparaffin, the monocyclic hydrocarbon of belt length side chain, are lubrications
Highly desirable existing component in oil composition.For linear paraffin, although have very high viscosity index (VI), ought when there are a lot,
It will affect the low temperature flow of lubricating oil, therefore, should be removed.The cyclic hydrocarbon of polycyclic short-side chain is to keep lubricating oil forfeiture excellent
The main component of viscosity temperature characteristic, therefore should also be removed.
Be hydrocracked-isomerization dewaxing group technology is that current production high-quality lube base oil is more mature and advanced
Technology.As new hydrocracking unit is built, there will be a large amount of high-quality hydrocracking tail oils, to expand III class of API basis
The production of oil meets the lubrication oil market demand and provides good condition.Be hydrocracked-isomerization dewaxing group technology is will to add hydrogen
Feedstock oil of the Cracking Unit hydrocracking tail oil produced as downstream isomerization dewaxing unit will be added by Isodewaxing Technology
Undesirable components in hydrogen cracking tail oil carry out isomerization and are converted into ideal composition, and are retained in base oil fractions to reach
The purpose for reducing pour point, makes that dewaxed oil pour point is substantially reduced and lube base oil yield with higher and viscosity refer to
Number.It follows that the hydrocracking catalyst that selection is suitable for produces the good hydrocracking tail oil and isomerization dewaxing list of viscosity temperature characteristic
First catalyst combination can produce high-quality lube base oil.
Y type molecular sieve is to be mutually communicated to be formed along three crystalline axis directions by twelve-ring by octahedral zeolite cage, is
A kind of excellent catalyst activity component, not only cracking activity is high, but also selectivity is good.Therefore the invention of Y type molecular sieve is being urged
Change field has epoch-making meaning.Since high silica alumina ratio Y type molecular sieve has good hydrothermal stability and absolute acid stability, it is
Main acid carrier in hydrocracking catalyst at present, and show irreplaceable role.
Nineteen eighty-three, patent USP4397827 is reported for the first time has synthesized ZSM-48 molecular sieve.ZSM-48 molecular sieve is a kind of
Molecular sieve with ten-ring cellular structure, aperture are 0.53nm × 0.56nm.Mobil company has applied for two in succession within 2009
The patent USP7482300 and USP7625478 of synthesis about low silica-alumina ratio ZSM-48 molecular sieve.The result of study table of patent
Bright ZSM-48 molecular sieve has good hydroisomerizing pour point depression ability.
Above two molecular sieve is combined with each other by chemically synthesized mode, is prepared into catalyst by modified,
Hydrocracking reaction process and isomerization reaction are carried out under same process conditions, realize raw material be hydrocracked with it is different
The combination of structure dewaxing, can produce high-quality lube base oil.The equipment investment of factory can be mitigated in this way, while may be used also
Two covering devices in production process are combined into set of device, the energy consumption of enterprise is reduced.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of ZSM-48/Y composite molecular screen, this is compound
Zeolite molecular sieve organically combines the isomery performance of ZSM-48 molecular sieve with the cracking performance of Y type molecular sieve, Ke Yiying
For producing High Quality Lube Base Oils in hydrocracked petroleum refining process.
The preparation method of ZSM-48/Y composite molecular screen of the invention, including following content:
(1) ZSM-48 molecular sieve is subjected to high-temperature roasting, then by the ZSM-48 molecular sieve after unsaturated olefin and roasting
It comes into full contact with, carries out roasting carbon deposit reaction in an inert gas atmosphere, then carry out ZSM-48 molecular sieve surface dealumination treatment, obtain
To -48 molecular sieve of modified ZSM-5；
(2) -48 molecular sieve powder of modified ZSM-5, silicon source, sodium hydroxide and water reaction mixture is uniformly mixing to obtain to coagulate
Colloid system, is aged 8 ~ 48 hours at 4 ~ 40 DEG C in confined conditions, then crystallization 12 ~ 72 hours at 80 ~ 120 DEG C, preferably
Crystallization 18 ~ 60 hours at 90 ~ 110 DEG C, finally cooling, washing, dry and roasting, obtain ZSM-48/Y composite molecular screen.
In the method for the present invention, ZSM-48 molecular sieve described in step (1) has the property that silica/alumina mole
Than between 25 ~ 100, specific surface area is 180 ~ 300m2Between 0.22 ~ 0.28ml/g of/g, Kong Rongwei.
In the method for the present invention, high-temperature roasting temperature described in step (1) is 350 ~ 650 DEG C, and the time is 1 ~ 12 hour.
In the method for the present invention, unsaturated olefin described in step (1) be the positive structure that carbon atom number is 2 ~ 10 or isomeric olefine,
Diene hydrocarbon mixture；Wherein the alkene and molecular sieve, which come into full contact with, refers to that unsaturated olefin diffuses into inside molecular sieve；
When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, when contact
Between 0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions are as follows: pressure 0.1 ~
1.0MPa, time of contact 0.5 ~ 4 hour, molecular sieve answered thorough impregnation in liquefied olefines.The alkene and molecular sieve are abundant
Contact generally carries out at normal temperature, and the unsaturated hydrocarbons state phase is phase under room temperature.
In the method for the present invention, inert gas described in step (1) is one of nitrogen, helium and argon gas, roasting product
The temperature of charcoal reaction is 450 ~ 650 DEG C, and the time is 1 ~ 8 hour.
In the method for the present invention, dealumination treatment process described in step (1) is as follows: by the ZSM-48 after carbon deposit reacts points
Son sieve is added in the nitric acid solution of 0.5 ~ 2.0mol/L, is then handled 0.5 ~ 2 hour, is washed out to pH at 40 ~ 90 DEG C
Value is less than 10；The mass ratio of water is 1:3 ~ 20 in the additional amount and solution of ZSM-48 molecular sieve,
In the method for the present invention, the molar ratio of step (2) each material (does not include -48 points of modified ZSM-5 in terms of following substance
Son sieve) ben(Na2O):n(Al2O3):n(H2O)=12~18:1:280~350；On the basis of reaction mixture gel system quality,
The additional amount of -48 molecular sieve of modified ZSM-5 is 10wt% ~ 30wt%, preferably 15wt% ~ 25wt%
In the method for the present invention, silicon source described in step (2) is one of aluminium chloride, aluminum sulfate, aluminum nitrate or sodium aluminate
Or several, preferred sodium aluminate.
In the method for the present invention, drying condition described in step (2) are as follows: drying temperature be 50 ~ 120 DEG C, drying time be 8 ~
24 hours.
In the method for the present invention, roasting condition described in step (2) are as follows: maturing temperature be 450 ~ 650 DEG C, calcining time be 1 ~
6 hours.
The ZSM-48/Y composite molecular screen of the method for the present invention preparation, has the property that with ZSM-48/Y composite molecular screen
On the basis of weight, Y type molecular sieve content is 40% ~ 90%, preferably 50% ~ 85%；Silica alumina ratio (this of ZSM-48/Y composite molecular screen
Silica alumina ratio described in the text is the molar ratio of silica and aluminium oxide) it is 10 ~ 45, preferably 20 ~ 40；Specific surface area be 350 ~
850m2/ g, preferably 450 ~ 750m2/g；Pore volume is 0.24 ~ 0.35ml/g, preferably 0.28 ~ 0.34ml/g.
Advantage is ZSM-48/Y composite molecular screen of the invention compared with prior art: first by ZSM-48 molecule
Sieve carries out carbon distribution, and the duct inside ZSM-48 molecular sieve is protected by carbon distribution, makes subsequent dealumination treatment only at ZSM-48 points
Son sieve surface carries out, and the molecular sieve surface defect silicon position by dealumination treatment is more exposed as silicon source, so that synthesis
The silicon source of the Y type molecular sieve of ZSM-48 molecular sieve surface growth, to obtain inlaying with ZSM-48 molecular sieve with Y type molecular sieve
ZSM-48/Y composite molecular screen together, the presence of mosaic texture avoids because stratum nucleare molecule is completely covered in shell molecular sieve
It sieves and reaction process is caused to hinder the progress of stratum nucleare hydrocracking reaction, ensure that two kinds of reaction process while progress, in this way
During the reaction ZSM-48/Y composite molecular screen can give full play to Y type molecular sieve cracking ability is strong and ZSM-48 molecular sieve
Hydrocracking reaction occurs on Y type molecular sieve, splits simultaneously for the good catalysis feature of isomerism ability, the reactants such as aromatic hydrocarbons and cycloalkane
In ZSM-48 molecular sieve isomerization reaction occurs for the linear paraffin solved in the hydro carbons and reactant generated, can be greatly reduced in product
Wax content.Experiment shows that composite molecular screen can be used in hydrocracked petroleum refining process producing high-quality lube base
The base oil wax content of oil, production is greatly reduced.
Detailed description of the invention
Fig. 1 is the composite molecular screen XRD diffraction pattern that the embodiment of the present invention 2 synthesizes.
Fig. 2 is the composite molecular screen SEM figure that the embodiment of the present invention 2 synthesizes.
Specific embodiment
Preparation process of the invention is further illustrated below with reference to embodiment, but following embodiment is not constituted to present invention side
The limitation of method.The conventional ZSM-48 molecular sieve for being added and there is following property: silica/alumina mole is all made of in preparation process
Than being 48, specific surface area 220m2/ g, Kong Rongwei 0.25ml/g.
Embodiment 1
(1) ZSM-48 molecular sieve is roasted 4 hours under the conditions of 550 DEG C, then the ZSM-48 molecular sieve after roasting exists
Thorough impregnation is in liquid C under the conditions of 0.3MPa10H18In 2 hours, then in nitrogen atmosphere, roasted under the conditions of 500 DEG C 2 small
The reaction of Shi Jinhang carbon deposit, the then (addition of molecular sieve in the nitric acid solution of 0.8mol/L by the ZSM-48 molecular sieve after carbon deposit
The mass ratio of amount and water in solution is 1:10) it is handled 1.0 hours at 80 DEG C, washing, less than 10, obtains modified ZSM-5-to pH value
48 molecular sieves；
(2) mixed liquor of -48 molecular sieve of modified ZSM-5 in step (1), sodium aluminate, sodium hydroxide and water is stirred evenly
Reaction mixture gel system is obtained, is aged 48 hours at 10 DEG C, then thermostatic crystallization 48 hours under the conditions of 100 DEG C, so
It is then 12 hours dry under the conditions of 90 DEG C by cooling, washing, it finally roasts 3 hours, finally obtains under the conditions of 550 DEG C
ZSM-48/Y composite molecular screen.Molecular sieve property such as table 1.
Reaction mixture molar ratio (removes -48 molecular sieve of modified ZSM-5) are as follows:n(Na2O):n(Al2O3):n(H2O)=15:1:
320.Wherein the additional amount of -48 molecular sieve of modified ZSM-5 accounts for the 11wt% of gel rubber system gross mass.
Embodiment 2
(1) ZSM-48 molecular sieve is roasted 6 hours under the conditions of 450 DEG C, then the ZSM-48 molecular sieve after roasting exists
Thorough impregnation is in liquid C under the conditions of 0.4MPa8H14In 1 hour, then in nitrogen atmosphere, roasted 4 hours under the conditions of 480 DEG C
Carry out carbon deposit reaction, then by the ZSM-48 molecular sieve after carbon deposit in the nitric acid solution of 1.5mol/L (the additional amount of molecular sieve
Mass ratio with water in solution is 1:8) it is handled 2.0 hours at 50 DEG C, washing, less than 10, obtains -48 points of modified ZSM-5 to pH value
Son sieve；
(2) mixed liquor of -48 molecular sieve of modified ZSM-5 in step (1), sodium aluminate, sodium hydroxide and water is stirred evenly
Reaction mixture gel system is obtained, is aged 24 hours at 30 DEG C, then thermostatic crystallization 36 hours under the conditions of 105 DEG C, so
It is then 12 hours dry under the conditions of 100 DEG C by cooling, washing, it finally roasts 4 hours, finally obtains under the conditions of 500 DEG C
ZSM-48/Y composite molecular screen.Molecular sieve property such as table 1.
Reaction mixture molar ratio (removes -48 molecular sieve of modified ZSM-5) are as follows:n(Na2O):n(Al2O3):n(H2O)=16:1:
300.Wherein the additional amount of -48 molecular sieve of modified ZSM-5 accounts for the 15wt% of gel rubber system gross mass.
Embodiment 3
(1) ZSM-48 molecular sieve is roasted 7 hours under the conditions of 480 DEG C, then the ZSM-48 molecular sieve after roasting exists
Under the conditions of 0.8MPa with C3H6Alkene contacts 1 hour, then in nitrogen atmosphere, roasts 2 hours and is accumulated under the conditions of 550 DEG C
Charcoal reaction, then by the ZSM-48 molecular sieve after carbon deposit in the nitric acid solution of 1.2mol/L (the additional amount and solution of molecular sieve
The mass ratio of middle water is 1:12) it is handled 1.5 hours at 75 DEG C, washing, less than 10, obtains -48 molecular sieve of modified ZSM-5 to pH value；
(2) mixed liquor of -48 molecular sieve of modified ZSM-5 in step (1), sodium aluminate, sodium hydroxide and water is stirred evenly
Reaction mixture gel system is obtained, is aged 36 hours at 20 DEG C, then thermostatic crystallization 60 hours under the conditions of 90 DEG C, then
It is then 12 hours dry under the conditions of 90 DEG C through cooling, washing, it finally roasts 5 hours, finally obtains under the conditions of 480 DEG C
ZSM-48/Y composite molecular screen.Molecular sieve property such as table 1.
Reaction mixture molar ratio (removes -48 molecular sieve of modified ZSM-5) are as follows:n(Na2O):n(Al2O3):n(H2O)=12:1:
340.Wherein the additional amount of -48 molecular sieve of modified ZSM-5 accounts for the 18wt% of gel rubber system gross mass.
Embodiment 4
(1) ZSM-48 molecular sieve is roasted 6 hours under the conditions of 520 DEG C, then the ZSM-48 molecular sieve after roasting exists
Under the conditions of 0.7MPa with C4H8Alkene mixture contacts 1.5 hours, and then in nitrogen atmosphere, it is small that 3 are roasted under the conditions of 500 DEG C
The reaction of Shi Jinhang carbon deposit, the then (addition of molecular sieve in the nitric acid solution of 0.8mol/L by the ZSM-48 molecular sieve after carbon deposit
The mass ratio of amount and water in solution is 1:8) it is handled 1.0 hours at 80 DEG C, washing, less than 10, obtains modified ZSM-5-48 to pH value
Molecular sieve；
(2) mixed liquor of -48 molecular sieve of modified ZSM-5 in step (1), sodium aluminate, sodium hydroxide and water is stirred evenly
Reaction mixture gel system is obtained, is aged 18 hours at 35 DEG C, then thermostatic crystallization 60 hours under the conditions of 100 DEG C, so
It is then 8 hours dry under the conditions of 90 DEG C by cooling, washing, it finally roasts 2 hours, finally obtains under the conditions of 600 DEG C
ZSM-48/Y composite molecular screen.Molecular sieve property such as table 1.
Reaction mixture molar ratio (removes -48 molecular sieve of modified ZSM-5) are as follows:n(Na2O):n(Al2O3):n(H2O)=14:1:
290.Wherein the additional amount of -48 molecular sieve of modified ZSM-5 accounts for the 20wt% of gel rubber system gross mass.
Embodiment 5
(1) ZSM-48 molecular sieve is roasted 4 hours under the conditions of 600 DEG C, then the ZSM-48 molecular sieve after roasting exists
Thorough impregnation is in liquid C under the conditions of 0.6MPa10H18In 1.5 hours, then in nitrogen atmosphere, roast 5 under the conditions of 460 DEG C
Hour carry out carbon deposit reaction, then by the ZSM-48 molecular sieve after carbon deposit in the nitric acid solution of 1.2mol/L (molecular sieve plus
The mass ratio for entering water in amount and solution is 1:15) it is handled 1.5 hours at 80 DEG C, washing, less than 10, is modified to pH value
ZSM-48 molecular sieve；
(2) mixed liquor of -48 molecular sieve of modified ZSM-5 in step (1), sodium aluminate, sodium hydroxide and water is stirred evenly
Reaction mixture gel system is obtained, is aged 28 hours at 30 DEG C, then thermostatic crystallization 48 hours under the conditions of 100 DEG C, so
It is then 12 hours dry under the conditions of 100 DEG C by cooling, washing, it finally roasts 3 hours, finally obtains under the conditions of 560 DEG C
ZSM-48/Y composite molecular screen.Molecular sieve property such as table 1.
Reaction mixture molar ratio (removes -48 molecular sieve of modified ZSM-5) are as follows:n(Na2O):n(Al2O3):n(H2O)=13:1:
330.Wherein the additional amount of -48 molecular sieve of modified ZSM-5 accounts for the 15wt% of gel rubber system gross mass.
Embodiment 6
Ion exchange: composite molecular screen prepared by embodiment is washed to neutrality, drying, then in 80 DEG C of water bath conditions
Under, ion exchange is carried out with 1mol/L ammonium nitrate, makes sodium oxide content less than 0.5%, is washed, drying in 550 DEG C of roasting 3h, obtains
To hydrogen type molecular sieve.
Hydro-thermal process: by hydrogen type molecular sieve, constant temperature handles 2h under the conditions of hydrothermal temperature is 580 DEG C respectively, obtains at hydro-thermal
Molecular sieve after reason.
Catalyst preparation: alumina powder, amorphous silicon aluminium, modified molecular screen powder are uniformly mixed, and it is molten that acid is then added
Liquid forms after sufficiently rolling, then 8 hours dry under the conditions of 100 DEG C, finally roasts 8 hours, obtains under the conditions of 600 DEG C
Catalyst carrier；The catalyst carrier that the metal impregnation solution of W and Ni impregnates is prepared, then dry 6 under the conditions of 120 DEG C
Hour, it is finally roasted 6 hours under the conditions of 470 DEG C, obtains hydrocracking catalyst.Catalyst property such as table 2.
Comparative example 1
With embodiment 6, the difference is that composite molecular screen to be replaced with to the mixing of ZSM-48 Yu Y type molecular sieve molecular sieve
Object obtains catalyst property such as table 2.
Comparative example 2
With embodiment 6, the difference is that composite molecular screen is replaced with Y type molecular sieve, catalyst property such as table is obtained
2.
Evaluating catalyst condition: evaluating apparatus is carried out using 200m1 small hydrogenation device, before activity rating to embodiment 1,
5 and comparative example 1,2 catalyst carry out presulfurization.The raw materials used oil nature of evaluation catalyst activity and reaction process condition are shown in Table
3 and table 4, catalyst reaction performance comparing result be shown in Table 5.When evaluating catalyst, feedstock oil first passes through Hydrobon catalyst (institute
The Hydrobon catalyst used then immediately proceeds to hydrocracking catalyst bed for FF-46) bed, urges by hydrofinishing
The organic nitrogen content controlled in feedstock oil when agent bed is lower than 15ppm.
The main character of 1 raw molecule of table sieve and the composite molecular screen of each embodiment preparation.
The composition of 2 catalyst of table.
3 process conditions of table.
4 feedstock property of table.
5 catalyst reaction performance of table.
| Catalyst | Embodiment 1 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Reaction temperature, DEG C | 381 | 383 | 386 | 384 |
| Wax content, wt% | 19 | 18 | 23 | 26 |
| Tail oil normal paraffin content, wt% | 9.1 | 7.8 | 11.8 | 14.1 |
Hydrocracking reaction the result shows that, the mixed object of composite molecular screen of the invention is compared, when conversion ratio is identical, instead
Answer temperature 3 ~ 5 DEG C low, the wax content and normal paraffin content of tail oil product are lower than comparative example.Illustrate prepared by the method for the present invention
Composite molecular screen have the characteristics that be hydrocracked that ability is good, hydroisomerization ability is strong.
Claims (13)
1. a kind of preparation method of ZSM-48/Y composite molecular screen, including following content: (1) ZSM-48 molecular sieve being carried out high temperature
Then unsaturated olefin and the ZSM-48 molecular sieve after roasting are come into full contact with, carry out roasting carbon deposit in an inert atmosphere by roasting
Then reaction carries out ZSM-48 molecular sieve surface dealumination treatment, obtains -48 molecular sieve of modified ZSM-5；(2) by -48 points of modified ZSM-5
Son sieve powder, silicon source, sodium hydroxide and water are uniformly mixing to obtain reaction mixture gel system, in confined conditions in 4 ~ 40
It is aged at DEG C 8 ~ 48 hours, then crystallization 12 ~ 72 hours at 80 ~ 120 DEG C, finally cooling, washing, dry and roasting obtain
ZSM-48/Y composite molecular screen.
2. according to the method for claim 1, it is characterised in that: ZSM-48 molecular sieve described in step (1) has following property
Matter: silica/alumina molar ratio is 25 ~ 100, and specific surface area is 180 ~ 300m20.22 ~ 0.28ml/g of/g, Kong Rongwei.
3. according to the method for claim 1, it is characterised in that: high-temperature roasting temperature described in step (1) is 350 ~ 650
DEG C, the time is 1 ~ 12 hour.
4. according to the method for claim 1, it is characterised in that: it is 2 that unsaturated olefin described in step (1), which is carbon atom number,
~ 10 positive structure or isomeric olefine, diene hydrocarbon mixture.
5. according to the method for claim 1, it is characterised in that: alkene described in step (1) comes into full contact with molecular sieve is
Refer to that unsaturated olefin diffuses into inside molecular sieve；When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve
Contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When using liquid unsaturated olefin, liquid is unsaturated
Alkene and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 hour, molecular sieve answered thorough impregnation in liquid
In state unsaturated olefin.
6. according to the method for claim 1, it is characterised in that: inert atmosphere described in step (1) be nitrogen, helium and
The temperature of one of argon gas, roasting carbon deposit reaction is 450 ~ 650 DEG C, and the time is 1 ~ 8 hour.
7. according to the method for claim 1, it is characterised in that: dealumination treatment process described in step (1) is as follows: will pass through
ZSM-48 molecular sieve after carbon deposit reaction is added in the nitric acid solution of 0.5 ~ 2.0mol/L, then handles 0.5 at 40 ~ 90 DEG C
It ~ 2 hours, is washed out to pH value less than 10；The mass ratio of water is 1:3 ~ 20 in the additional amount and solution of ZSM-48 molecular sieve.
8. according to the method for claim 1, it is characterised in that: in step (2) molar ratio of each material in terms of following substance,
Forn(Na2O):n(Al2O3):n(H2O)=12 ~ 18:1:280 ~ 350 do not include -48 molecular sieve of modified ZSM-5.
9. according to the method for claim 1, it is characterised in that: in step (2), be with reaction mixture gel system quality
Benchmark, the additional amount of -48 molecular sieve of modified ZSM-5 are 10wt% ~ 30wt%.
10. according to the method for claim 1, it is characterised in that: silicon source described in step (2) is aluminium chloride, aluminum sulfate, nitre
One or more of sour aluminium or sodium aluminate.
11. according to the method for claim 1, it is characterised in that: drying condition described in step (2) are as follows: drying temperature is
50 ~ 120 DEG C, drying time is 8 ~ 24 hours.
12. according to the method for claim 1, it is characterised in that: roasting condition described in step (2) are as follows: maturing temperature is
450 ~ 650 DEG C, calcining time is 1 ~ 6 hour.
13. according to ZSM-48/Y composite molecular screen prepared by method described in claim 1 ~ 12 any claim, feature
It is to have the property that on the basis of ZSM-48/Y composite molecular screen weight, Y type molecular sieve content is 40% ~ 90%； ZSM-
The silica alumina ratio of 48/Y composite molecular screen is 10 ~ 45；Specific surface area is 350 ~ 850m2/ g, pore volume are 0.24 ~ 0.35ml/g；Institute
State the molar ratio that silica alumina ratio is silica and aluminium oxide.
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